CN113717225A - High-viscosity phosphate and preparation method, application and composition thereof - Google Patents
High-viscosity phosphate and preparation method, application and composition thereof Download PDFInfo
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- CN113717225A CN113717225A CN202111151874.3A CN202111151874A CN113717225A CN 113717225 A CN113717225 A CN 113717225A CN 202111151874 A CN202111151874 A CN 202111151874A CN 113717225 A CN113717225 A CN 113717225A
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 49
- 239000010452 phosphate Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title abstract description 27
- 239000010720 hydraulic oil Substances 0.000 claims abstract description 26
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003063 flame retardant Substances 0.000 claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims abstract description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 3
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000011347 resin Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 28
- -1 phosphate ester Chemical class 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 230000003078 antioxidant effect Effects 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002199 base oil Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- 230000007797 corrosion Effects 0.000 claims description 5
- 230000009970 fire resistant effect Effects 0.000 claims description 5
- 229910019213 POCl3 Inorganic materials 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical group 0.000 claims description 4
- 239000013556 antirust agent Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl chloride Substances ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- VXZJUYUVOQZBNU-UHFFFAOYSA-N phosphoric acid 1,2-xylene Chemical compound P(=O)(O)(O)O.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C.CC1=C(C=CC=C1)C VXZJUYUVOQZBNU-UHFFFAOYSA-N 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 239000000047 product Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 11
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000001965 increasing effect Effects 0.000 description 9
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000002269 spontaneous effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000010687 lubricating oil Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000196 viscometry Methods 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000326 densiometry Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000011545 laboratory measurement Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010913 used oil Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3229—Esters of aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/048—Mixtures of base-materials and additives the additives being a mixture of compounds of unknown or incompletely defined constitution, non-macromolecular and macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
- C10M2223/0415—Triaryl phosphates used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/08—Resistance to extreme temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
Abstract
The invention relates to the technical field of high-temperature flame-retardant phosphate hydraulic oil, in particular to high-viscosity phosphate and a preparation method, application and a composition thereof, wherein the structure of the high-viscosity phosphate is shown as the formula (I):
in the formula I, R1、R2、R3、R4Each independently selected from phenyl substituted with 1-5 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or unsubstituted phenyl; r is C2‑20An alkylene group of (a); the invention also provides a preparation method and application of the high-viscosity phosphate, a composition of the high-viscosity phosphate and a preparation method of the composition.
Description
Technical Field
The invention belongs to the technical field of high-temperature phosphate flame-retardant hydraulic oil, and particularly relates to high-viscosity phosphate and a preparation method, application and composition thereof.
Background
The phosphate flame-retardant hydraulic oil is widely applied to hydraulic systems of electric power, military and airplanes, has extremely strong flame-retardant performance, and has an irreplaceable position in the hydraulic systems which are in contact with high-temperature heat sources and naked flames. With the use of a large amount of high-capacity and high-parameter steam turbine units, the single-machine capacity of a thermal power plant reaches over 800MW, which puts higher requirements on the flame resistance, high-temperature wear resistance, high-temperature oxidation resistance and the like of phosphate flame-resistant hydraulic oil. In particular, the use temperature increases, and high-viscosity hydraulic oil is required to ensure a good lubricating oil film at the friction part.
At present, the widely used phosphate flame-retardant hydraulic oil is ISO VG32 and VG46 phosphate flame-retardant hydraulic oil, and the following problems exist: firstly, the flame resistance is poor, and the spontaneous combustion point is generally below 550 ℃; secondly, the oil film strength is not enough under the high-temperature use condition, and the problems of large abrasion and short service life of equipment are caused; and thirdly, the antioxidant property is poor, the aging and deterioration are rapid, and the oil change period is short. In order to solve the above-mentioned disadvantages of the phosphate flame-retardant hydraulic oil, it is necessary to use a phosphate flame-retardant hydraulic oil having a higher viscosity. However, it is difficult to achieve ISO VG46 or higher for commercial phosphate base oils due to the steric hindrance of the phosphate ester. At present, in order to increase the viscosity of phosphate flame-retardant hydraulic oil, a method of adding a tackifier is mainly adopted. However, due to the structural characteristics of phosphate and the index requirements of phosphate flame-retardant hydraulic oil, the existing tackifier cannot meet the requirements, such as common PMA (polymethacrylate), OCP (acrylonitrile-propylene-styrene copolymer) and PIB (acrylonitrile-butadiene-styrene copolymer) tackifiers which are poor in compatibility with phosphate, and can cause the problems of reduced density, poor air release value, reduced self-ignition point and the like.
In order to solve the problems of the existing tackifier, the applicant invents a high-performance phosphate flame-retardant hydraulic oil tackifier which has the characteristics of similar structure and good compatibility with phosphate, can improve the oxidation stability and high-temperature wear resistance of phosphate flame-retardant hydraulic oil and the like, and can meet the use requirements of a high-temperature hydraulic system.
Disclosure of Invention
The invention aims to solve the problems of density reduction, poor air release value, low self-ignition point and the like caused by poor compatibility of the tackifier and phosphate ester which are widely used at present. The phosphate ester serving as the tackifier can be used for preparing phosphate ester flame-retardant hydraulic oil with different viscosity grades, has the characteristics of good compatibility, high spontaneous combustion point, good oxidation stability, good high-temperature wear resistance and the like, and can meet the use requirements of a high-temperature and high-pressure hydraulic system.
In order to achieve the technical purpose, the invention provides the following technical scheme: a high viscosity phosphate ester has a structure represented by formula (I):
in the formula I, R1、R2、R3、R4Each independently selected from phenyl substituted with 1-5 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or unsubstituted phenyl;
r is C2-20An alkylene group of (a).
Further, said R1、R2、R3、R4At least one is a 4-isopropylphenyl group;
still further, said R1、R2、R3、R4Up to three are 4-isopropylphenyl groups;
r is
Further, said R1、R2、R3、R4Each independently selected from phenyl, 4-methylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl;
r is
The invention also provides a preparation method of the phosphate ester, which comprises the following steps:
a)
POCl3reacting with dihydroxy compound in the presence of perfluorosulfonic acid resin to obtain a compound shown as a formula (II);
b)
reacting the compound of formula (II) with a monohydroxy compound in the presence of a perfluorosulfonic acid resin to obtain a compound of formula (I), each group being as defined above.
Further, step a is embodied as POCl3Heating the dihydroxy compound and the dihydroxy compound to 90-100 ℃ in the presence of perfluorosulfonic acid resin for reaction for 1-2h, and then heating to 110-130 ℃ for reaction for 1-2h to obtain a compound (II);
the step b is to heat the compound of the formula (II) and the monohydroxy compound to 150 ℃ in the presence of the perfluorosulfonic acid resin for 2-3h, then heat to 150 ℃ and 160 ℃ for 1-2h, and obtain the compound of the formula (I) through post treatment.
The invention also provides the use of a high viscosity phosphate ester as described above for a fire resistant hydraulic oil composition.
Further, use of the high viscosity phosphate ester as a viscosity increasing agent in phosphate flame-retardant hydraulic oil.
The present invention also provides a flame-retardant hydraulic oil comprising the high-viscosity phosphate ester according to any one of claims 1 to 3.
Further, the flame-retardant hydraulic oil has the following composition:
base oil: 50-100 parts;
antioxidant: 0.1-1 part;
antirust agent: 0.1-0.5 part;
corrosion inhibitor: 0.01-0.1 part;
the high-viscosity phosphoric acid ester according to any one of claims 1 to 3: 1-50 parts;
the base oil is tert-butyl triphenyl phosphate or tri (xylene) phosphate or a mixture of the tert-butyl triphenyl phosphate and the tri (xylene) phosphate;
the antioxidant is amine antioxidant or phenol antioxidant or the mixture of the amine antioxidant and the phenol antioxidant;
further, the amine antioxidant is T534 type; the phenolic antioxidant is T501 type, L135 type or the mixture of the two;
further, the antirust agent is T705 type or T711 type or a mixture of the two; the corrosion inhibitor is T706 type.
The invention also provides a preparation method of the anti-flaming hydraulic oil, which comprises the steps of mixing the components according to the proportion, adding activated clay and/or activated carbon, heating to 145-155 ℃, preserving heat for 1-3 hours, and filtering to obtain the product.
Further, the dosage of the activated clay is 5 percent of the total weight of the mixture; the amount of the active carbon is 1 percent of the total weight of the mixture.
Due to the adoption of the technology, compared with the prior art, the invention has the remarkable advantages that:
1) the high-viscosity phosphate ester has excellent compatibility with common phosphate ester base oil, has excellent flame resistance and viscosity increasing property, and can effectively solve the problems of density reduction, poor air release value, low spontaneous combustion point and the like caused by poor compatibility of the tackifier and the phosphate ester which are widely used at present;
2) the phosphate ester flame-retardant hydraulic oil prepared by using the high-viscosity phosphate ester has high spontaneous combustion point (higher than 600 ℃), strong oxidation resistance (has strong acid capture capacity, can effectively inhibit the increase of acid value, can keep the volume resistivity of the hydraulic oil stable), can obviously improve the anti-wear extreme pressure performance, and can effectively prolong the service life of equipment.
Detailed Description
In order to make the technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments.
Example 1
(1) 5mol POC13(766.65g), 1mol of neopentyl glycol (104.15g), and 1g of a perfluorosulfonic acid resin (perfluorosulfonic acid resin HNF-5W manufactured by Jiangyun Seisaku Co., Ltd.) were put in a 2L four-neck flask equipped with a stirrer, a thermometer, and a reflux tube at a time; and then raising the reaction temperature to 95-100 ℃ within 30min, keeping the temperature for 1h, raising the temperature to 110-130 ℃ within 35-45 min, and reacting for 2 h. After the reaction was completed, excess POCl was distilled off under a vacuum of-0.01 MPa3。
(2) Supplementing 1g of perfluorosulfonic acid resin into the distilled product, gradually adding 572g of 4-isopropylphenol (5% excess) at 105-110 ℃, and finishing the addition within 30 min. After the addition, the temperature is increased to 140-150 ℃, the reaction is carried out for 3 hours, and then the temperature is increased to 150-160 ℃ for 2 hours. Carrying out vacuum distillation on the reacted product to remove unreacted neopentyl glycol and a low-boiling-point product so as to obtain a crude product; then adding a proper amount of 1, 2-dichloroethane into the product, filtering to remove the perfluorosulfonic acid resin, neutralizing with 2% Na0H aqueous solution until the solution is weakly alkaline, and finally washing with deionized water until the solution is neutral. Separating the organic layer, vacuum distilling to remove solvent and water to obtain viscous phosphate ester product with yield of 97.1% and purity of 99.2%, LC-MS (ESI) and M/z 672[ M + H ]]+. The basic properties are shown in Table 1.
Example 2
(1) 5mol POC13(766.65g), 1mol of neopentyl glycol (104.15g), and 1g of a perfluorosulfonic acid resin (perfluorosulfonic acid resin HNF-5W manufactured by Jiangyun Seisaku Co., Ltd.) were put in a 2L four-neck flask equipped with a stirrer, a thermometer, and a reflux tube at a time; and then raising the reaction temperature to 95-100 ℃ within 30min, keeping the temperature for 1h, raising the temperature to 110-130 ℃ within 35-45 min, and reacting for 2 h. After the reaction was completed, excess POCl was distilled off under a vacuum of-0.01 MPa3。
(2) And supplementing 1g of perfluorosulfonic acid resin into the distilled product, and gradually and sequentially adding 272.38g of 4-isopropylphenol and 227.1g of p-cresol (5 percent excess) at 105-110 ℃ within 30 min. After the addition, the temperature is increased to 140-150 ℃, the reaction is carried out for 3 hours, and then the temperature is increased to 150-160 ℃ for 2 hours. Carrying out vacuum distillation on the reacted product to remove unreacted neopentyl glycol and a low-boiling-point product so as to obtain a crude product; then adding a proper amount of 1, 2-dichloroethane into the product, filtering to remove the perfluorosulfonic acid resin, neutralizing with 2% Na0H aqueous solution until the solution is weakly alkaline, and finally washing with deionized water until the solution is neutral. Separating the organic layer, vacuum distilling to remove solvent and water to obtain viscous phosphate ester product, LC-MS (ESI) M/z 616[ M + H ]]+. The basic properties are shown in Table 1.
Example 3
(1) 5mol POC13(766.65g), 1mol of neopentyl glycol (104.15g), and 1g of a perfluorosulfonic acid resin (perfluorosulfonic acid resin HNF-5W manufactured by Jiangyun Seisaku Co., Ltd.) were put in a 2L four-neck flask equipped with a stirrer, a thermometer, and a reflux tube at a time; then the reaction temperature is increased to 95 to 30minKeeping the temperature at 100 ℃ for 1h, then increasing the temperature to 110-130 ℃ within 35-45 min, and reacting for 2 h. After the reaction was completed, excess POCl was distilled off under a vacuum of-0.01 MPa3。
(2) And supplementing 1g of perfluorosulfonic acid resin into the distilled product, gradually adding a mixture of 108g of p-cresol, 136.19g of 4-isopropylphenol and 150.22g of p-tert-butylphenol at 105-110 ℃, adding a mixture of 98.7 g of phenol (5% excess) after the addition is finished, and finishing the addition within 30 min. After the addition, the temperature is raised to 140-150 ℃, the reaction is carried out for 3h, and then the temperature is raised to 150-160 ℃ for 2 h. Carrying out vacuum distillation on the reacted product to remove unreacted neopentyl glycol and a low-boiling-point product so as to obtain a crude product; then adding a proper amount of 1, 2-dichloroethane into the product, filtering to remove the perfluorosulfonic acid resin, neutralizing with 2% Na0H aqueous solution until the solution is weakly alkaline, and finally washing with deionized water until the solution is neutral. The organic layer was separated and the solvent and water were removed by vacuum distillation to give a viscous phosphate product (major product I-1 and minor product I-2 by HPLC analysis) in 93.1% yield and 99.6% purity. The basic properties are shown in Table 1.
Example 4
(1) 5mol POC13(766.65g), 1mol of neopentyl glycol (104.15g), and 1g of a perfluorosulfonic acid resin (perfluorosulfonic acid resin HNF-5W manufactured by Jiangyun Seisaku Co., Ltd.) were put in a 2L four-neck flask equipped with a stirrer, a thermometer, and a reflux tube at a time; and then raising the reaction temperature to 95-100 ℃ within 30min, keeping the temperature for 1h, raising the temperature to 110-130 ℃ within 35-45 min, and reacting for 2 h. After the reaction was completed, excess POCl was distilled off under a vacuum of-0.01 MPa3。。
(2) 1g of perfluorosulfonic acid resin is added into the distilled product, 136.19g of 4-isopropylphenol and 335.3g of p-cresol (5 percent excess) are sequentially added step by step at 105-110 ℃, and the addition is finished within 30 min. After the addition, the temperature is raised to 140-150 ℃, the reaction is carried out for 3h, and then the temperature is raised to 150-160 ℃ for 2 h. Carrying out vacuum distillation on the reacted product to remove unreacted neopentyl glycol and a low-boiling-point product so as to obtain a crude product; then adding a proper amount of 1, 2-dichloroethane into the product, filtering to remove the perfluorosulfonic acid resin, neutralizing with 2% Na0H aqueous solution until the solution is weakly alkaline, and finally washing with deionized water until the solution is neutral. Separating the organic layer, vacuum distilling to remove solvent and water to obtain viscous phosphate ester product with yield of 92.5% and purity of 99.1%, LC-MS (ESI) of M/z 588[ M + H ]]+. The basic properties are shown in Table 1.
Example 5
(1) 5mol POC13(766.65g), 1mol of neopentyl glycol (104.15g), and 1g of a perfluorosulfonic acid resin (perfluorosulfonic acid resin HNF-5W manufactured by Jiangyun Seisaku Co., Ltd.) were put in a 2L four-neck flask equipped with a stirrer, a thermometer, and a reflux tube at a time; and then raising the reaction temperature to 95-100 ℃ within 30min, keeping the temperature for 1h, raising the temperature to 110-130 ℃ within 35-45 min, and reacting for 2 h. After the reaction was completed, excess POCl was distilled off under a vacuum of-O.01MPa3。。
(2) 1g of perfluorosulfonic acid resin is added into the distilled product, 454.2g of p-cresol (5 percent excess) is added at 105-110 ℃, and the addition is completed within 30 min. After the addition, the temperature is raised to 140-150 ℃, the reaction is carried out for 3h, and then the temperature is raised to 150-160 ℃ for 2 h. The product after reaction is vacuumizedDistilling to remove unreacted neopentyl glycol and low-boiling-point products to obtain a crude product; then adding a proper amount of 1, 2-dichloroethane into the product, filtering to remove the perfluorosulfonic acid resin, neutralizing with 2% Na0H aqueous solution until the solution is weakly alkaline, and finally washing with deionized water until the solution is neutral. Separating the organic layer, vacuum distilling to remove solvent and water to obtain viscous phosphate ester product with yield of 89.9% and purity of 98.7%, LC-MS (ESI) of M/z 560[ M + H ]]+. The basic properties are shown in Table 1.
Example 6
The phosphate ester products prepared in examples 1-5 were tested for performance and the results are shown in Table 1.
TABLE 1 tackifier Performance test results
| Item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| *Kinematic viscosity at 40 ℃ in mm2/s | 3113.5 | 2219.3 | 2737.1 | 2536.6 | 1093.2 |
| Flash point, DEG C | 301 | 312 | 307 | 310 | 257 |
Testing was performed according to kinematic viscometry and kinetic viscometer algorithms for petroleum products described in GB/T265.
Examples 7 to 14
Adding base oil, additive, tackifier, active clay (5% of the total amount) and active carbon (1% of the total amount) into a blending kettle, heating to 120 +/-5 ℃, keeping the temperature for 2 hours, and filtering to obtain the product.
The preparation method is as above, and the formula composition is shown in the table.
TABLE 2 specific formulation compositions for examples 7-14
| Composition (in parts) | Example 7 | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 | Example 14 |
| BPDP | 78 | 76 | 78 | 78 | -- | 42 | 77 | 79 |
| TXP | -- | -- | -- | -- | 87 | 42 | -- | -- |
| Example 1 | 22 | -- | -- | -- | -- | -- | -- | -- |
| Example 2 | -- | 24 | -- | -- | -- | -- | -- | -- |
| Example 3 | -- | -- | 22 | -- | -- | -- | -- | -- |
| Example 4 | -- | -- | -- | 22 | 13 | 16 | -- | -- |
| Example 5 | -- | -- | -- | -- | -- | -- | 10 | 13 |
| PIB(PB2400) | -- | -- | -- | -- | -- | -- | 13 | -- |
| PMA(V8-310) | -- | -- | -- | -- | -- | -- | -- | 8 |
| Antioxidant L135 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antirust agent T711 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Corrosion inhibitor T706 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 | 0.05 |
The results of the performance testing of examples 7-14 are shown in Table 3.
TABLE 3 results of the Performance test of examples 7 to 14
The relevant test method criteria in the table are: kinematic viscosity at 40 ℃: GB/T265 (kinematic and kinetic viscometry of petroleum products);
self-ignition point: DL 706 (power plant fire resistant oil auto ignition point determination method);
volume resistivity: DL/T421 (electricity is measured by volume resistivity of used oil);
air release value: SH/T0308 (lubricating oil air Release value assay);
density at 20 ℃: GB/T1884 (crude oil or liquid petroleum products Density laboratory measurements (densitometry);
the diameter of the abrasion marks: SH/T0189 (a method for testing the antiwear performance of lubricating oil (a four-ball machine method);
oxidation test: EN 14832 (method for measuring oxidation stability).
As can be seen from table 2: the embodiment has the advantages of high spontaneous combustion point, large volume resistivity, small air release value, good wear resistance and better oxidation resistance (the acid value is increased slightly after an oxidation test, and the corrosion to copper and steel is small).
The above-mentioned embodiments are merely preferred embodiments of the present invention, and should not be construed as limiting the present invention, and the scope of the present invention should be defined by the claims, and equivalents including technical features of the claims, i.e., equivalent modifications within the scope of the present invention.
Claims (10)
1. A high viscosity phosphate ester is characterized in that the structure is shown as formula (I):
in the formula I, R1、R2、R3、R4Each independently selected from phenyl substituted with 1-5 methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl or unsubstituted phenyl;
r is C2-20An alkylene group of (a).
2. The phosphate ester according to claim 1, wherein R is1、R2、R3、R4At least one is a 4-isopropylphenyl group;
r is
3. The phosphate ester according to claim 1 or 2, wherein R is1、R2、R3、R4Each independently selected from phenyl, 4-methylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl;
r is
4. The preparation method of phosphate ester according to claim 1, comprising the following specific steps:
a)
POCl3reacting with dihydroxy compound in the presence of perfluorosulfonic acid resin to obtain a compound shown as a formula (II);
b)
reacting a compound of formula (II) with a monohydroxy compound in the presence of a perfluorosulfonic acid resin to give a compound of formula (I), each group being as defined in claim 1.
5. The method of claim 4, wherein step a is specifically POCl3Heating the dihydroxy compound and the dihydroxy compound to 90-100 ℃ in the presence of perfluorosulfonic acid resin for reaction for 1-2h, and then heating to 110-130 ℃ for reaction for 1-2h to obtain a compound (II);
the step b is to heat the compound of the formula (II) and the monohydroxy compound to 150 ℃ in the presence of the perfluorosulfonic acid resin for 2-3h, then heat to 150 ℃ and 160 ℃ for 1-2h, and obtain the compound of the formula (I) through post treatment.
6. Use of the high viscosity phosphoric acid ester according to any one of claims 1 to 3 for a flame-retardant hydraulic oil composition.
7. A flame-retardant hydraulic oil comprising the high-viscosity phosphate ester according to any one of claims 1 to 3.
8. The fire resistant hydraulic oil of claim 7, wherein the fire resistant hydraulic oil has a composition of:
base oil: 50-100 parts;
antioxidant: 0.1-1 part;
antirust agent: 0.1-0.5 part;
corrosion inhibitor: 0.01-0.1 part;
the high-viscosity phosphoric acid ester according to any one of claims 1 to 3: 1-50 parts;
the base oil is tert-butyl triphenyl phosphate and/or tri (xylene) phosphate;
the antioxidant is an amine antioxidant and/or a phenol antioxidant.
9. The preparation method of the fire-resistant hydraulic oil as claimed in claim 7, wherein the components are mixed according to the proportion, activated clay and/or activated carbon are added, the mixture is heated to 145-155 ℃ and is kept for 1-3 hours, and the product is obtained by filtration.
10. The process of claim 8 wherein the amount of activated clay used is 5% by weight of the total mixture; the amount of the active carbon is 1 percent of the total weight of the mixture.
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